Refractory object and process of forming a glass sheet using the refractory object

ABSTRACT

A refractory object can include at least approximately 10 wt % Al 2 O 3  and at least approximately 1 wt % SiO 2 . In an embodiment, the refractory object can include an additive. In a particular embodiment, the additive can include TiO 2 , Y 2 O 3 , SrO, BaO, CaO, Ta 2 O 5 , Fe 2 O 3 , ZnO, or MgO. The refractory object can include at least approximately 3 wt % of the additive. In an additional embodiment, the refractory object can include no greater than approximately 8 wt % of the additive. In a further embodiment, the creep rate of the refractory object can be at least approximately 1×10 −6  h −1 . In another embodiment, the creep rate of the refractory object can be no greater than approximately 5×10 −5  h −1 . In an illustrative embodiment, the refractory object can include a glass overflow trough or a forming block.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application claims priority under 35 U.S.C. § 120 and is adivisional of U.S. application Ser. No. 14/984,539, entitled “RefractoryObject and Process of Forming a Glass Sheet Using The RefractoryObject,” by Olivier Citti et al., filed Dec. 30, 2015, now U.S. Pat. No.9,902,653, which in turn claims priority under 35 U.S.C. § 120 to and isa continuation of U.S. application Ser. No. 13/738,988 entitled“Refractory Object and Process of Forming a Glass Sheet Using theRefractory Object,” by Olivier Citti et al., filed Jan. 10, 2013, nowU.S. Pat. No. 9,249,043, which in turn claims priority from U.S.Provisional Patent Application No. 61/585,618, filed Jan. 11, 2012,entitled “Refractory Object and Process of Forming a Glass Sheet Usingthe Refractory Object”, naming inventors Olivier Citti et al., which allapplications are assigned to the current assignee hereof and areincorporated by reference herein in their entireties.

FIELD OF THE DISCLOSURE

This disclosure is directed to refractory objects including glassoverflow troughs and glass forming blocks, and a process of using therefractory object.

BACKGROUND

Alkali alumino-silicate glasses are being used in applications wheremechanical performance is important. These glasses can be formed using afusion draw process. In a fusion draw process, liquid glass flows overone or more lips of a glass overflow trough and the liquid glass fusesat the bottom of the glass overflow trough to form a glass sheet. Theglass overflow trough can be made from a forming block including analuminum material. The size and quality of a glass sheet may be limitedby physical properties of the glass overflow trough used to form theglass sheet. In addition, the lifetime of a glass overflow trough can beaffected by its physical properties. Further improvement of refractoryblocks used to make forming blocks and glass overflow troughs isdesired.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure may be better understood, and its numerousfeatures and advantages made apparent to those skilled in the art byreferencing the accompanying drawings.

FIG. 1 is a diagram illustrating a particular embodiment of a refractoryobject.

FIG. 2 is a diagram illustrating a particular embodiment of a glassoverflow trough formed from a refractory object.

FIG. 3 is a diagram illustrating a particular set of variouscross-sectional perspectives of glass overflow troughs.

FIG. 4 is a diagram illustrating the formation of a particular glasssheet from the glass overflow trough.

The use of the same reference symbols in different drawings indicatessimilar or identical items.

DETAILED DESCRIPTION

The following description in combination with the figures is provided toassist in understanding the teachings disclosed herein. The followingdiscussion will focus on specific implementations and embodiments of theteachings. This focus is provided to assist in describing the teachingsand should not be interpreted as a limitation on the scope orapplicability of the teachings.

FIG. 1 is a diagram illustrating a particular embodiment of a refractoryobject 100. The refractory object 100 can be a refractory block 102having a rectilinear shape with a thickness (t), a width (w), and aheight (h). In an embodiment, any of the dimensions t, w, or h can be atleast approximately 0.02 m, at least approximately 0.05 m, at leastapproximately 0.11 m, at least approximately 0.5 m, at leastapproximately 1.1 m, at least approximately 2.0 m, at leastapproximately 4.0 m, or more. In the embodiment as illustrated in FIG.1, the refractory block 102 can be a forming block from which a glassoverflow trough can be formed. A forming block as used herein refers toa sintered ceramic material that can be shaped to provide a glassoverflow trough.

The refractory block 102 can be formed from a number of startingmaterials. In an embodiment, the refractory block 102 can be formedusing one or more metal oxides, one or more additives, one or moreadditional materials, or a combination thereof. In a particularembodiment, a metal oxide used as starting material for the refractoryblock 102 can include Al₂O₃ and SiO₂. In an embodiment, the Al₂O₃ can beprovided as a powder. The Al₂O₃ powder can be in the form of particleshaving an averaged particle size no greater than approximately 100micrometers, an averaged particle size no greater than approximately 30micrometers, an averaged particle size no greater than approximately 20micrometers, or an averaged particle size no greater than approximately15 micrometers. In another embodiment, the averaged particle size is atleast approximately 0.5 micrometers, at least approximately 1.0micrometers, or at least approximately 5.0 micrometers.

In an embodiment, a combination of Al₂O₃ powders having differentparticle sizes can be used. For example, the number of differentparticle sized Al₂O₃ powders can be two, three, four, or more. In aparticular embodiment, Al₂O₃ powders having two different particle sizesare used. In a more particular embodiment, one of the Al₂O₃ powders canhave an averaged particle size that is less than approximately 50%, lessthan approximately 40%, or less than approximately 30% of the averagedparticle size of the other Al₂O₃ powder. To illustrate, one of the Al₂O₃powders can have a nominal particle size of 2 micrometers, and the otherAl₂O₃ powder can have a nominal particle size of 10 micrometers. TheAl₂O₃ powders of different particle sizes can be mixed in any ratio. Forexample, Al₂O₃ powders having two different particle sizes can be mixedin a ratio of approximately 1:99, approximately 2:98, approximately3:97, approximately 10:90, approximately 20:80, approximately 50:50,approximately 80:20, approximately 90:10, approximately 97:3,approximately 98:2, or approximately 99:1. Likewise, mixture of Al₂O₃powders having three or more different sizes can be prepared in aparticular ratio.

In an embodiment, Al₂O₃ can be provided as reactive Al₂O₃, non-reactiveAl₂O₃, or any combination thereof. Reactive Al₂O₃ can help to increasethe density and reduce the porosity of the refractory object 100. Asused herein, “reactive Al₂O₃” is intended to mean that the particularAl₂O₃ powder has a surface area of at least two square meters per gram 2m²/g), and, “non-reactive Al₂O₃” is intended to mean that the particularAl₂O₃ powder has a surface area less than two square meters per gram (<2m²/g). In an embodiment, the amount of reactive Al₂O₃, as a fraction oftotal Al₂O₃ powder used to form the refractory object 100 can include atleast approximately 1% and may be up to 100% of the total Al₂O₃ powderused. A combination of reactive Al₂O₃ and non-reactive Al₂O₃ powders canbe used. In a particular embodiment, at least approximately 2%, at leastapproximately 5%, at least approximately 16%, at least approximately25%, or at least approximately 50% of the Al₂O₃ used in forming therefractory object 100 can be provided as reactive Al₂O₃. In anotherembodiment, no greater than approximately 95%, no greater thanapproximately 90%, no greater than approximately 75%, no greater thanapproximately 60%, or no greater than approximately 50% of the Al₂O₃used in forming the refractory object 100 is provided as reactive Al₂O₃.

In another embodiment, at least a portion of the Al₂O₃ can be providedas mullite. In a particular embodiment, the mullite can include at leastapproximately 62% by weight (hereinafter “wt %”) Al₂O₃, at leastapproximately 66 wt % Al₂O₃, or at least approximately 71 wt % Al₂O₃.Additionally, the mullite may include no greater than approximately 78wt % Al₂O₃, no greater than approximately 74 wt % Al₂O₃, or no greaterthan approximately 68 wt % Al₂O₃.

At least a portion of the SiO₂ can be provided as mullite, amorphousSiO₂, crystalline SiO₂, talc, glass frit, or any combination thereof. Inan embodiment, the crystalline SiO₂ can be provided as quartz,tridymite, cristobalite, or any combination thereof. In an additionalembodiment, a glass frit used to provide SiO₂ to the refractory object100 can have SiO₂ content of at least approximately 55 wt % and be froman alkali free glass. In a further embodiment, mullite used to producethe refractory object 100 can include at least approximately 22 wt %SiO₂, at least approximately 24 wt % SiO₂, or at least approximately 26wt % SiO₂. In another embodiment, the mullite may also include nogreater than approximately 24 wt % SiO₂, no greater than approximately27 wt % SiO₂, or no greater than approximately 29 wt % SiO₂. In anadditional embodiment, talc used to produce the refractory object 100can include at least approximately 36 wt % SiO₂, at least approximately44 wt % SiO₂, or at least approximately 52 wt % SiO₂. In anotherembodiment, the talc may include no greater than approximately 54 wt %SiO₂, no greater than approximately 61 wt % SiO₂, or no greater thanapproximately 66 wt % SiO₂.

The starting materials for the refractory object 100 can also includeZr. In a particular embodiment, the Zr can be provided as an oxide, suchas ZrO₂. In another embodiment, the Zr can be provided as ZrSiO₄. Inaddition, the starting materials can include one or more additives. Theadditives can be a molecular compound including Ti, Y, Sr, Ba, Ca, Ta,Fe, Zn, Mg, or any combination thereof. In an embodiment, the additivescan be provided as an oxide, a carbide, a carbonate, a nitrate, asulfate, a halide, a phosphate, or any combination thereof. In addition,one or more additives can be provided as an oxide in combination with aboride, carbide, carbonate, nitrate, halide, phosphate, sulfate, or thelike. The one or more additives can have an oxidation state, such asM²⁺, M³⁺, M⁴⁺, M⁵⁺, or any combination thereof, where M is Ti, Y, Sr,Ba, Ca, Ta, Fe, Zn, or Mg.

In an embodiment, the additives can be provided in a substantially pureform with trace amounts of impurities. In another embodiment, one ormore additives can be provided as a compound. For example, MgO and TiO₂can be provided as an MgTiO₃ compound.

In a particular embodiment, at least a portion of the one or moreadditives can be provided as a powder. In a more particular embodiment,the powder may be in the form of particles having an averaged particlesize no greater than approximately 30 micrometers, no greater thanapproximately 20 micrometers, or no greater than approximately 15micrometers. In another embodiment, the averaged particle size is atleast approximately 0.1 micrometers, at least approximately 0.5micrometers, or at least approximately 1 micrometer.

In an embodiment, at least a portion of a particular additive can be asintering agent. In a particular example, the sintering agent can helpto reduce porosity by lowering a melting temperature of SiO₂ used tomake the refractory block 102 and allowing SiO₂ to be disposed withinpores of the refractory block 102. Reducing porosity of the refractoryobject can help to improve resistance to corrosion if the refractoryobject is later exposed to a corrosive environment. An exemplarysintering agent can include Ta, Ti, Fe, Mg, Zn, another suitablesintering agent, or any combination thereof. In an illustrativeembodiment, additives provided as sintering agents can be provided asoxides.

In another embodiment, at least a portion of a particular additive canbe added to react with SiO₂ to prevent Al from reacting with the SiO₂.In particular, Mg, Ca, Ba, Sr, Y, or any combination thereof, can beadded to react with SiO₂ rather than Al that is provided as a startingmaterial for the refractory block 100. In one embodiment, an additiveprovided to substitute for Al can be provided as an oxide. In anotherembodiment, an additive provided to substitute for Al can be provided asa silicate, such as mullite (Al₆Si₂O₁₃), talc (Mg₃SiO₁₀(OH)₂), yttriumsilicate (Y₂Si₂O₇) or any combination thereof. In a further embodiment,an Al substitute additive can be provided as an aluminosilicate, such ascordierite (Mg₂Al₄Si₅O₁₈), anorthite (CaA₁₂Si₂O₈), or any combinationthereof. In an additional embodiment, the Al replacement additive can beprovided as an aluminate, such as yttrium aluminum garnet (Y₃Al₅O₁₂),spinel (MgAl₂O₄), or any combination thereof.

Additional material that can be used to form the refractory block 102can include a binder, a solvent, a dispersant, a thickener, adeflocculant, another suitable ingredient, or any combination thereof.In an embodiment, the additional material can include non-metalliccompounds. In another embodiment, the additional material can include anorganic compound, water, or the like.

The starting materials and any additional materials can be combined andshaped to form a green body having a particular shape. Shaping can beperformed using a technique, such as slip casting, isostatic pressing,or any combination thereof. The shape can be rectilinear, cylindrical,spherical, ellipsoidal or nearly any other shape. In a particularembodiment, the green body can be in the shape of a rectilinear blockreferred to as a blank that can subsequently be machined to form a glassoverflow trough. In another embodiment, the green body can be structuredin such fashion to more closely match the final refractory object toreduce the extent of any further machine processing. For example, whenthe refractory object 100 includes a glass overflow trough, the shape ofthe green body may more closely resemble the glass overflow trough toreduce the amount of subsequent machining and ceramic material thatwould be discarded. More particularly, the green body can have arectilinear portion adjacent to a tapered portion. The rectilinearportion has a tapered region corresponding to a region where a glassoverflow trough will be formed. In another embodiment, the green bodycan be shaped to have the glass overflow trough adjacent to the taperedportion

After the green body is formed, the green body is heated in an oven,heater, furnace, or the like to form the refractory block 102 thatincludes a sintered ceramic material. The heating process can include aninitial heating where moisture, a solvent, or another volatile componentis evaporated, organic material is vaporized, or any combinationthereof. The initial heating can be conducted at a temperature in arange of approximately 100° C. to approximately 300° C. for a timeperiod in a range of approximately 10 hours to approximately 200 hours.Following the initial heating, the sintering can be performed at atemperature in a range of approximately 1400° C. to 1700° C. for a timeperiod in a range of approximately 10 hours to approximately 100 hoursto form the refractory block 102.

The shape of the refractory block 102 generally corresponds to the shapeof the green body. Thus, the refractory block 102 may have any of theshapes as previously described with respect to the green body. Duringsintering, some shrinkage may occur, and the refractory block 102 may besmaller than the green body.

A sintered object, such as the refractory block 102, can bedistinguished from objects that have been formed by fuse-casting. Inparticular, objects that have been formed by fuse-casting often includea highly abundant intergranular glass phase that fills the network ofcrystallized grains of the object. In contrast, a sintered object caninclude phases that are formed at the grain boundaries with anotherphase. Due to differences in their microstructures, the problemsencountered by sintered objects and by fused-cast objects in theirrespective applications and the technical solutions adopted for solvingthem are generally different. Furthermore, due to the differencesbetween manufacturing an object by sintering and manufacturing an objectby fuse-casting, a composition developed for a fused-cast product maynot be used a priori for manufacturing a sintered product,

In an embodiment, the refractory block 102 can include at leastapproximately 20 wt % Al₂O₃, at least approximately 50 wt % Al₂O₃, atleast approximately 70 wt % Al₂O₃, at least approximately 85 wt % Al₂O₃,at least approximately 90 wt % Al₂O₃, or at least approximately 92 wt %Al₂O₃. In another embodiment, the refractory block 102 may include nogreater than approximately 95 wt % Al₂O₃, no greater than approximately94 wt % Al₂O₃, no greater than approximately 93 wt % Al₂O₃, or nogreater than approximately 90 wt % Al₂O₃. In an additional embodiment,the refractory block 102 can include at least approximately 1.1 wt %SiO₂, at least approximately 1.5 wt % SiO₂, at least approximately 2.1wt % SiO₂, or at least approximately 2.7 wt % SiO₂. In a furtherembodiment, the refractory block 102 may include no greater thanapproximately 7 wt % SiO₂, no greater than approximately 6 wt % SiO₂, orno greater than approximately 4 wt % SiO₂.

The refractory block 102 can include an additive. In an embodiment, theadditive can include TiO₂, Y₂O₃, SrO, BaO, CaO, Ta₂O₅, Fe₂O₃, ZnO, orMgO. In a particular embodiment, the refractory block 102 can include atleast approximately 0.2 wt % of the additive. In an additionalembodiment, the refractory block 102 may include no greater thanapproximately 8 wt % of the additive. In a more particular embodiment,the refractory block 102 can include at least approximately 0.2 wt % ofthe additive, at least approximately 0.4 wt % of the additive, or atleast approximately 0.6 wt % of the additive. In another embodiment, therefractory block 102 may include no greater than approximately 8 wt % ofthe additive, no greater than approximately 7 wt % of the additive, orno greater than approximately 6 wt % of the additive.

In an embodiment, the additive is a particular additive of a pluralityof additives of the refractory block 102. In a particular embodiment,the refractory block 102 comprises at least approximately 0.3 wt % ofeach additive of the plurality of additives, at least approximately 0.8wt % of each additive of the plurality of additives, at least 1.6 wt %of each additive of the plurality of additives, or at least 2.5 wt % ofeach additive of the plurality of additives. In a particular embodiment,the refractory block 102 comprises at least approximately 5 wt % of theparticular additive. Additionally, a total content of the plurality ofadditives in the refractory block 102 is at least approximately 1.5 wt%, at least approximately 3 wt %, at least approximately 5 wt %, or atleast approximately 7 wt %. Further, a total content of the plurality ofadditives in the refractory block 102 may be no greater thanapproximately 14 wt %, no greater than approximately 12 wt %, or nogreater than approximately 10 wt %.

In an embodiment, the refractory block 102 includes TiO₂. In aparticular embodiment, the refractory object 102 includes at leastapproximately 0.2 wt % TiO₂, at least approximately 0.4 wt % TiO₂, or atleast 0.6 wt % TiO₂. In another embodiment, the refractory block 102includes no greater than approximately 4.0 wt % TiO₂, no greater thanapproximately 3.0 wt % TiO₂, or no greater than approximately 2.0 wt %TiO₂.

The refractory block 102 can also include MgO as an additive. In anembodiment, the refractory block 102 includes at least approximately 0.2wt % MgO, at least approximately 0.4 wt % MgO, or at least approximately0.6 wt % MgO. In another embodiment, the refractory block 102 mayinclude no greater than approximately 4.5 wt % MgO, no greater thanapproximately 3.5 wt % MgO, or no greater than approximately 2.5 wt %MgO. In still another embodiment, the refractory block 102 can includeCaO. In particular, the refractory block 102 can include at leastapproximately 0.2 wt % CaO, at least approximately 0.5 wt % CaO, or atleast approximately 0.7 wt % CaO.

In an embodiment, the refractory block 102 includes Fe₂O₃ as anadditive. In a particular embodiment, the refractory block 102 includesat least approximately 0.2 wt % Fe₂O₃, at least approximately 0.7 wt %Fe₂O₃, or at least approximately 0.9 wt % Fe₂O₃. In another embodiment,the refractory block 102 includes Ta₂O₅ as an additive. In anillustrative embodiment, the refractory block 102 includes at leastapproximately 0.2 wt % Ta₂O₅, at least approximately 0.4 wt % Ta₂O₅, orat least approximately 0.6 wt % Ta₂O₅. In an additional embodiment, therefractory block 102 may include no greater than approximately 2.0 wt %Ta₂O₅, no greater than approximately 1.1 wt % Ta₂O₅, or no greater thanapproximately 0.7 wt % Ta₂O₅.

The refractory block 102 can also include Y₂O₃ as an additive. In anembodiment, the refractory block 102 can include at least approximately1 wt % Y₂O₃, at least approximately 2 wt % Y₂O₃, or at leastapproximately 3 wt % Y₂O₃. In an additional embodiment, the refractoryblock 102 may include no greater than approximately 8 wt % Y₂O₃, nogreater than approximately 7 wt % Y₂O₃, or no greater than approximately6 wt % Y₂O₃.

In an embodiment, the refractory block 102 can include a single additiveor a particular combination of additives. In a particular embodiment,the refractory block 102 can include TiO₂ as an only additive of therefractory block 102. In another embodiment, the refractory block 102can include TiO₂ and MgO as additives. In a further embodiment, therefractory block can include TiO₂, Fe₂O₃, and Ta₂O₅. The refractoryblock 102 can also include Ta₂O₅ as an only additive or the refractoryblock 102 can include Y₂O₃ as an only additive.

In a particular embodiment, the refractory block 102 includes ZrO₂. Forexample, the refractory block 102 may include no greater thanapproximately 0.3 wt % ZrO₂, no greater than approximately 0.2 wt %ZrO₂, no greater than approximately 0.05 wt % ZrO₂, or is substantiallyfree of ZrO2. As used herein, the term “substantially free” refers tocontent of a particular material that is no more than trace amounts,such as no greater than 100 ppm by weight. In another embodiment, therefractory block 102 can include at least 0.03 wt % ZrO₂, at least 0.1wt % ZrO₂, or at least 0.25 wt % ZrO₂. In a more particular embodiment,the refractory block 102 can include an amount of Y₂O₃ that correspondsto the amount of ZrO₂ in the refractory block 102. To illustrate, therefractory block 102 can includes at least approximately 0.2 wt % ZrO₂and at least approximately 0.2 wt % Y₂O₃. In an additional embodiment,an amount of Y₂O₃ of the refractory block 102 can be provided to preventZrO₂ in the refractory block 102 from changing crystalline states.

The refractory block 102 can be machined to produce a different shape, asmoother surface, or both. In the illustrative embodiment of FIG. 2, therefractory block 102 can be machined to form a glass overflow trough200. The glass overflow trough 200, which is also a refractory object,has a body that includes a glass overflow trough portion 202 and atapered portion 204. The glass overflow trough portion 202 includes atrough that has a depth that decreases along a length of the glassoverflow forming block 200. FIG. 3 includes a cross-sectional view ofexemplary shapes of the tapered portion 204. More particularly, thetapered portion can include a wedge shape 2042, a concave shape 2044, ora convex shape 2046. Other shapes may used to meet the needs or desiresfor a particular application.

The refractory block 102 may have one or more physical properties thatare particularly suited for providing a glass overflow trough 200 thatis used to form glass that includes aluminum, silicon, alkalis (e.g. Na,K), earth alkalis (e.g. Ca, Ba, Sr), or any combination thereof (“Al—Siglass”). In particular, the physical properties of the refractory block102 can increase the lifetime of a glass overflow trough formed from therefractory block 102 by reducing corrosion. Lower corrosion of therefractory block 102 can help to maintain the mechanical integrity ofthe refractory block 102. Corrosion of the refractory block 102 can bereduced when the refractory block 102 has at least a particulartheoretical density and no greater than a particular apparent porosity.Further, when the refractory block 102 includes a glass overflow trough,lower corrosion may reduce the amount of the material from the glassoverflow trough migrating into the glass being formed using the glassoverflow trough and allow better control over the composition of theglass sheets formed using the glass overflow trough. Reducing corrosionof the refractory block 102 can also substantially prevent the formationof defects such as cords or knots. Corrosion of the refractory block 102can decrease when the percentage of the theoretical density is above aparticular value and/or when the apparent porosity of the refractoryblock 102 is above a particular value. Additionally, when the refractoryblock 102 has a particular theoretical density and no greater than aparticular apparent porosity and the refractory block 102 includes aglass overflow trough, an amount of glass material penetrating pores ofthe refractory block 102 can be reduced. This can also result in reduceddefects of the glass sheet being formed.

Further, minimization of creep rate of the refractory block 102 canprovide a minimum sag deformation when the refractory block 102 includesa glass overflow trough. Sag deformation as used herein can refer todeformation of the refractory block 102 due to the forces applied fromthe combined weight of the refractory block 102 and the glass sheetsbeing formed using the refractory block 102. Minimum sag deformation canallow a glass overflow trough to be used to produce glass sheets havingthicknesses no greater than a particular amount (e.g. no greater thanapproximately 1 mm) and having at least a particular length (e.g. atleast approximately 2 m).

In an embodiment, the refractory block 102 can have a fracture toughnessthat is at least approximately 2.1 MPa-m^(1/2), at least approximately2.5 MPa-m^(1/2), or at least approximately 2.9 MPa-m^(1/2). The fracturetoughness of the refractory block 102 can be measured according to anindentation test. In a particular embodiment, the fracture toughness canbe measured by an indentation fracture method according to ASTM E384-89as of the date of filing of this patent application with an applied loadof 0.5 kg. Increased fracture toughness of the refractory block 102 canminimize cracks of the refractory block 102 that may form during heatingof the refractory block 102.

In another embodiment, a quality of a glass contact interface withrespect to the refractory block 102 can be measured. In particular, avariation of the ASTM C621-09 Standard Test Method for IsothermalCorrosion Resistance of Refractories to Molten Glass as of the date offiling this patent application can be used. In an illustrativeembodiment, one or more samples having dimensions of 10×10×50 mm³ areprepared. The samples are hung inside an electric box furnace. Aplatinum crucible is filled with an amount of glass cullets (e.g. 50 gof alkali alumino-silicate glass) and the crucible is then placed intothe furnace. The filled crucible and the sample are heated up to atesting temperature (e.g. 1200° C.), while the sample remains hangingabove the glass. At the testing temperature the sample is lowered intothe molten glass and a bottom portion of the sample is attached to a topfixture of the set up and immersed into the melt a particular distance(e.g. about 30 mm) for about 120 hours at the testing temperature. Thesample is then raised outside of the glass at the testing temperatureand the sample and crucible are cooled. After cooling, the sample is cutin half along its longest dimension and both halves are polished. Theglass-sample interface is observed with a stereomicroscope. Theinterface can be qualified as “loose” when the sample has dissolved intothe glass melt and/or when pieces of the sample fell into the glassmelt. A loose interface leads to glass defects such as cords and stones(primary or recrystallized) that negatively impact glass production(i.e. yield and quality). The interface can be qualified as “tight” whenthere is a clear interface between the glass and the sample with noobvious reaction, in the glass or in the sample. Refractory objectshaving a tight glass contact performance can be used to produce highquality glass with a good yield.

Furthermore, blistering performance of the refractory block 102 can bemeasured. In an embodiment, a sample is prepared having dimensions of5×25×25 mm³. Glass cullets weighing about 5 g are placed on the topsurface of the sample. The sample topped with the glass cullets isheated in an electric box furnace up to 1200° C. at a rate of 5 to 10°C./min. The sample with the glass cullets is kept at a temperature of1200° C. for 16 hours. The sample is then cooled at a rate of about 20°C./min to avoid devitrification of the glass upon cooling. A number ofbubbles formed into the glass is observed using a stereomicroscope. Theblistering level is reported “high” when a particular number of bubblesis observed, such as at least 20 bubbles. The blistering level is “low”when no bubbles are observed or no greater than a particular number ofbubbles are observed in the glass, such as less than 20 bubbles andpreferably no greater than 10 bubbles. Blisters often cause glass sheetsto be rejected in most glass forming operations and minimization ofblistering is desired.

Additionally, a percentage of the theoretical density (“Th.D”) of therefractory block 102 can be measured. In an embodiment, the percentageof the theoretical density of the refractory block 102 may be no greaterthan approximately 98%, no greater than approximately 97%, or no greaterthan approximately 96%. In another embodiment, the percentage of thetheoretical density of the refractory object 102 can be at leastapproximately 91%, at least approximately 92%, or at least approximately93%. The theoretical density as referred to herein is the density asample would have if its porosity (open and closed) was equal to 0. Thepercentage of theoretical density, also referred to herein asdensification, for a given sample can be calculated from the ratio ofits density (“D”) over its theoretical density as shown in Equation 1:(D/Th.D.)×100=% Th.D.(densification)  (Eq. 1)When the refractory block 102 includes a number of oxides, thetheoretical density of a refractory block 102 can be calculated based onthe chemical composition of the mix of oxides included in the refractoryblock as shown in Equation 2:W _(dry)/[W _(Ox1) /Th.D _(Ox1) +W _(Ox2) /Th.D _(Ox2) + . . . +W _(Oxn)/Th.D _(Oxn)]=Th.D  (Eq. 2)where, W_(dry) is a dry weight of the mix of oxides, W_(Ox) is a weightof a particular oxide, and Th.D_(Ox) is the theoretical density of aparticular oxide.

Additionally, density as referred to herein is the ratio between themeasured weight of a sample of a refractory block and its volume withoutthe open porosity. The volume is measured by immersion of the sampleinto water having a density d_(Liq). This method can be referred to asthe immersion density method or Archimedes method and comprises thefollowing steps: (1) samples are vacuumed to eliminate air and adsorbedwater from the surface and from open pores (2) samples are immersed inwater to fill up open pores (3) the weight of the samples is measured(W_(imm)) immersed in water (4) samples are removed from the liquid andthe surface is wiped prior to measuring the weight of samples in airthis time (W_(wet)) (5) samples are dried and their weight is measured(W_(dry)). Equations 3 and 4 shown below can be used to calculate thedensity of the sample.(W _(dry) −W _(imm))/d _(Liq) =V(volume of sample)  (Eq. 3)W _(dry) /V=D  (Eq. 4)

Further, the apparent porosity of the refractory block 102 can bemeasured. In a particular embodiment, the apparent porosity of therefractory block 102 may be no greater than approximately 1.0 vol %, nogreater than approximately 0.8 vol %, no greater than approximately 0.5vol %, or no greater than approximately 0.2 vol %. Open (or apparent)porosity as used herein is the volume of porosity that is accessible(i.e. the volume that can be filled). Apparent porosity is expressedherein as a percentage of total volume as shown by Equation 5, where thevolume of the pores (V_(poro)) is calculated according to Equation 6:(V _(poro) /V)×100=% Poro  (Eq. 5)(W _(wet) −W _(dry))/d _(Liq) =V _(Poro)  (Eq. 6)

A creep rate of the refractory block 102 can also be measured. The creeprate can be a flexural creep rate. The flexural creep rate is ameasurement of the rate of deflection of a refractory object in adirection normal to the length of the refractory when the refractoryobject has been subjected to a predetermined mechanical stress at apredetermined temperature for a predetermined time period. In anembodiment, the creep rate of the refractory block 102 may be no greaterthan approximately 1.0×10⁻⁴ h⁻¹, no greater than approximately 5.0×10⁻⁵h⁻¹, no greater than approximately 7.5×10⁻⁶ h⁻¹, no greater thanapproximately 4.9×10⁻⁶ h⁻¹, or no greater than approximately 1.01×10⁻⁶h⁻¹. In another embodiment, the creep rate of the refractory block 102can be at least approximately 2.00×10⁻⁶ h⁻¹, at least approximately8.00×10⁻⁶ h⁻¹, or at least approximately 1.00×10⁻⁵ h⁻¹. In a particularembodiment, the creep rate is measured using a 4-point bending setupwhere the distance between the outer supports is approximately 80 mmwhile the inner supports are approximately 40 mm apart. An 8×9×100 mmsurface ground bar of the material to test is placed on the bottomsupports and a stress of approximately 2 MPa was applied through the topfixture. The test is conducted at a temperature of approximately 1275°C. for approximately 50 hours. The deflection of the bar as a functionof time is recorded during the whole test, and the deformation of thebar is then calculated. In a particular embodiment, the Hollenberg modelcan be used to calculate the deformation of the bar from the deflectionof the bar, as described in “Calculation of Stresses and Strains in FourPoint Bending Creep Tests,” by G. W. Hollenberg et al., J. Am. Ceram.Soc., Vol. 54, N^(o) 6, p 196-199 (1971).

The refractory block 102 can include grains having an averaged size nogreater than approximately 500 micrometers, no greater thanapproximately 300 micrometers, or no greater than approximately 110micrometers. In another embodiment, the grains of the refractory block102 can include grains having an averaged size of at least approximately10 micrometers, at least approximately 30 micrometers, or at leastapproximately 50 micrometers. The grain size is estimated from theobservation of polished sections of the refractory block 102 and themeasurement of the length (maximum dimension) and width (minimumdimension) of a large number of single grains (at least 100 grainsrandomly chosen). The averaged grain size can be determined using thewidths, lengths, or a combination thereof, for example an average of theaverage width and average length (i.e., (average width+averagelength)/2) of the grains. In an embodiment, the averaged grain size canbe based on an average of widths of the grains, an average of lengths ofthe grains, a median value corresponding to the width or the length, orthe like. When comparing grain sizes, lengths of a sample are comparedto the lengths of another sample or a prior art composition, widths of asample are compared to the widths of another sample or a prior artcomposition, and a median value for grains of a sample are to becompared to the median values for grains of another sample or a priorart composition.

In another embodiment, size distributions can be determined from thedata collected on the grains as previously described with respect to theaverage lengths and widths. As used herein, a D10 value represents the10^(th) percentile, a D50 value represents the 50^(th) percentile, and aD90 value represents the 90^(th) percentile. Thus, D50 corresponds tothe median value. In an embodiment where length is used as the basis ofgrain size, the D10, the D50 value, the D90 value, or a combinationthereof, for the size of the grains of the refractory block 102 may beno greater than approximately 450 micrometers, no greater thanapproximately 300 micrometers, or no greater than approximately 150micrometers. In an additional embodiment where length is used as thebasis of grain size, the D10, the D50 value, the D90 value, or acombination thereof, for the size of the grains of the refractory block102 is at least approximately 5 micrometers, at least approximately 20micrometers, or at least approximately 50 micrometers.

The distribution of grain sizes within the sintered ceramic material canhave a single mode or a plurality of modes, such as two, three, four,etc. In an embodiment, the sintered ceramic material can have a bimodaldistribution of averaged grain sizes. In a particular embodiment, one ofthe modes can have an averaged grain size that is less thanapproximately 50%, less than approximately 40%, or less thanapproximately 30% of the averaged grain size of the other mode.

Furthermore, the refractory block 102 can have one or more phases, suchas an aluminum phase and a silica phase. In a particular embodiment,substantially all of the aluminum of the refractory block 102 can bedisposed in the aluminum phase. In another embodiment, when therefractory block 102 includes one or more additives, any one or more ofthe additives can be disposed within each of the aluminum phase and thesilica phase. In an additional embodiment, substantially all of any oneor more of the additives of the refractory block 102 can be disposedoutside of the aluminum phase. In a more particular embodiment,substantially all of any one or more of the additives can be disposedwithin the silica phase. In a further embodiment, the silica phase issubstantially uniformly dispersed throughout the aluminum phase within abody portion of the refractory block 102. In still another embodiment,the refractory block 102 includes a peripheral region disposed betweenan edge of the refractory block 102 and the body portion and outside ofthe body portion, where any portion of the peripheral region may bewithin no greater than approximately 20 mm of an edge of the refractoryblock 102, no greater than approximately 10 mm of the edge of therefractory object, no greater than approximately 5 mm of the edge of therefractory object, or no greater than approximately 1 mm of the edge ofthe refractory block 102.

In an embodiment, the silica phase includes an aluminum silicate, amagnesium silicate, a calcium silicate, a barium silicate, a strontiumsilicate, an yttrium silicate, or any combination thereof. In aparticular embodiment, the refractory block 102 includes no greater thanapproximately 1.0 wt % of an alkali metal oxide (e.g. Na₂O, K₂O), nogreater than approximately 0.5 wt % of the alkali metal oxide, nogreater than approximately 0.3 wt % of the alkali metal oxide, nogreater than approximately 0.3 wt % of the alkali metal oxide, or issubstantially free of any alkali metal oxide. In a more particularembodiment, substantially all of the alkali metal oxide, if present, iswithin the silica phase. In a further embodiment, one or more additivesdisposed within the silica phase can affect the melting point of thesilica phase. The melting point of the silica phase can be at leastapproximately 1300° C., at least approximately 1400° C., at leastapproximately 1500° C., at least approximately 1600° C., or at leastapproximately 1700° C. In another embodiment, the melting point of thesilica phase is greater than at least approximately a sinteringtemperature used in forming the refractory object.

The refractory block 102, when in the form of a glass overflow formingblock, can be useful in forming a glass sheet by a fusion process. FIG.4 includes a perspective view of the glass overflow forming block duringthe formation of a glass sheet 302. The glass overflow forming block isheated to a temperature in a range of approximately 1050 C toapproximately 1300° C. The glass overflow forming block includes theglass overflow trough portion 202 and the tapered portion 204, aspreviously described. In the embodiment as illustrated, the glassoverflow forming block also includes end guards 206 that generallydefine the width of the glass sheet 302 to be formed. The glass overflowforming block further includes an inlet port 208 that receives a moltenglass composition. A trough within the glass overflow trough portion 202receives the molten glass composition until the trough fills up.Thereafter, the molten glass composition flows over at least one of thelips of the glass overflow trough portion 202. The molten glasscomposition then flows along opposite outer surfaces of the glassoverflow trough portion 202 and the tapered portion 204. At the end ofthe tapered portion 204 that is opposite the glass overflow troughportion 202, the molten glass composition along the opposite outersurfaces fuse together to form the glass sheet 302. In anotherembodiment, another type of glass object may be formed.

In an embodiment, the glass sheet 302 can have a thickness of at leastapproximately 20 micrometers, at least approximately 30 micrometers, orat least approximately 50 micrometers. In another embodiment, the glasssheet 302 may have a thickness no greater than approximately 5 mm, nogreater than approximately 3 mm, or no greater than approximately 1.1mm. With respect to the width, the process allows the end guards 206 tobe set to permit any desired width of the glass sheet 302. For example,the glass sheet 302 can have a width of at least approximately 0.5 m, atleast approximately 1.1 m, at least approximately 2.0 m, at leastapproximately 4.0 m, or larger.

Many different aspects and embodiments are possible. Some of thoseaspects and embodiments are described herein. After reading thisspecification, skilled artisans will appreciate that those aspects andembodiments are only illustrative and do not limit the scope of thepresent invention.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims. Numerical values in this Examples section may be approximated orrounded off for convenience.

Refractory objects including a variety of different sintered ceramicmaterials are prepared using the process described previously and anumber of starting materials, such as alumina powders, silica,particular additives, other materials, or a combination thereof. Tables1 to 6 include the compositions of the samples, all of which areprincipally alumina containing. Trace levels of impurities may bepresent but are not reported, as such impurities typically do notsignificantly affect the performance of such samples. In addition, thetotal % of the components shown for each of the samples may not be 100%due to rounding.

The samples are tested to determine apparent porosity and a percentageof theoretical density as described previously. In addition, fracturetoughness, 4-point creep rate, glass contact interface, blisteringperformance, or a combination thereof, are measured for particularsamples shown in Table 7 according to the processes previouslydescribed.

Table 1 includes samples having MgO, CaO, TiO₂, or a combinationthereof, as an additive. The starting materials for the samples includean amount of reactive Al₂O₃, an amount of non-reactive Al₂O₃, or both.For example, Samples 1, 2, and 3 are prepared with 94.00 wt % reactiveAl₂O₃. In addition, Sample 4 is prepared with 24.63 wt % reactive Al₂O₃and 73.89 wt % non-reactive Al₂O₃.

MgTiO₃ is added as a starting material for some samples shown inTable 1. For example, Sample 3 is prepared with 2.0 wt % MgTiO₃. TheMgTiO₃ used to prepare Sample 16 of Table 1 includes 33.2 wt % MgO, 66.2wt % TiO₂, and the remainder comprising amounts of Al₂O₃, SiO₂, ZrO₂,BaO, Fe₂O₃, P₂O₅, CaO, Na₂O, and K₂O. In addition, Sample 4 is preparedwith 1.0 wt % MgO. Talc is also provided as a starting material for somesamples in Table 1. To illustrate, Sample 1 is prepared with 6.0 wt %talc, Sample 2 is prepared with 5.0 wt % talc, and Sample 3 is preparedwith 4.0 wt % talc. The talc used to prepare the Samples of Table 1includes 74.86 wt % Al₂O₃, 24.7 wt % SiO₂, and a remainder includingamounts of TiO₂, Fe₂O₃, CaO, MgO, Na₂O, K₂O, and P₂O₅.

TABLE 1 % % Name Al₂O₃ SiO₂ MgO CaO TiO₂ Other Th. D porosity Sample 193.81 3.23 1.83 0.23 0.60 0.13 92 0.00 Sample 2 93.81 2.70 1.86 0.201.16 0.12 90 0.22 Sample 3 93.81 2.16 1.90 0.17 1.72 0.11 90 0.31 Sample4 98.10 0.01 1.00 0.01 0.49 0.25 83 16.44

Table 2 includes samples having TiO₂, Ta₂O₅, or a combination thereof,as an additive. The starting materials for the samples include an amountof reactive Al₂O₃, an amount of non-reactive Al₂O₃, or both. Forexample, Sample 5 is prepared with 19.99 wt % reactive Al₂O₃ and 64.01wt % non-reactive Al₂O₃, Sample 6 is prepared with 19.99 wt % reactiveAl₂O₃ and 59.01 wt % non-reactive Al₂O₃, and Sample 7 is prepared with19.99 wt % reactive Al₂O₃ and 59.01 wt % non-reactive Al₂O₃.

Furthermore, Samples 5, 6, and 7 are prepared with an amount of mullite.To illustrate, Sample 5 is prepared with 15.0 wt % mullite, and Samples6 and 7 are prepared with 20.0 wt % mullite. The mullite used to prepareSamples 5 and 6 is CE Minerals Mullite 70-325 including 67.39 wt %Al₂O₃, 28.38 wt % SiO₂, 2.7 wt % TiO₂, 1.10 wt % Fe₂O₃, and a remaindercomprised of CaO, MgO, Na₂O, K₂O, and P₂O₅. The mullite used to prepareSample 7 is Duramul 325/F Mullite including 74.86 wt % Al₂O₃, 24.70 wt %SiO₂, and a remainder comprised of TiO₂, Fe₂O₃, CaO, MgO, Na₂O, K₂O, andP₂O₅. Additionally, Samples 5, 6, and 7 are prepared with 1 wt % Ta₂O₅and Sample 27 is prepared with 0.9 wt % Ta₂O₅.

TABLE 2 % % Name Al₂O₃ SiO₂ TiO₂ Ta₂O₅ Other Th. D porosity Sample 593.75 4.27 0.41 1.00 0.42 95 0.20 Sample 6 92.14 5.69 0.55 1.00 0.47 950.20 Sample 7 93.64 4.95 0.01 1.00 0.29 92 0.40

Table 3 includes samples having Y₂O₃ as an additive. The startingmaterials for the samples include an amount of reactive Al₂O₃, an amountof non-reactive Al₂O₃, or both. For example, Samples 8, 9, and 10 areprepared with 94.00 wt % reactive Al₂O₃. Additionally, Sample 11 isprepared with 19.98 wt % reactive Al₂O₃ and 65.03 wt % non-reactiveAl₂O₃.

Furthermore, Sample 11 is prepared with an amount of mullite. Toillustrate, Sample 11 is prepared with 12.0 wt % mullite. The mulliteused to prepare Sample 11 is Duramul 325/F Mullite including 74.86 wt %Al₂O₃, 24.70 wt % SiO₂, and a remainder comprised of TiO₂, Fe₂O₃, CaO,MgO, Na₂O, K₂O, and P₂O₅.

Sample 8 is prepared with 6 wt % Y₂O₃, Sample 9 is prepared with 4 wt %Y₂O₃, Sample 10 is prepared with 5 wt % Y₂O₃, and Sample 11 is preparedwith 3 wt % Y₂O₃. Further, Sample 8 is prepared with 2.0 wt % amorphousSiO₂ and Sample 9 is prepared with 1.0 wt % crystalline SiO₂.

TABLE 3 % % Name Al₂O₃ SiO₂ Y₂O₃ TiO₂ Other Th. D porosity Sample 893.81 0.02 6.00 0.00 0.16 86 12.53 Sample 9 93.83 1.99 4.00 0.00 0.16 920.28 Sample 10 93.82 1.01 5.00 0.00 0.16 94 0.20 Sample 11 93.62 2.983.00 0.01 0.28 94 0.21

Table 4 includes samples having ZrO₂. The starting materials for thesamples include an amount of reactive Al₂O₃. For example, Sample 12 isprepared with 92.50 wt % reactive Al₂O₃, and Sample 13 is prepared with92.00 wt % reactive Al₂O₃. Additionally, Sample 12 is prepared with 1.5wt % MgTiO₃ and 6.0 wt % talc. Sample 13 is prepared with 3.0 wt % ZrO₂,3.0 wt % Ta₂O₅, 1.0 wt % Y₂O₃, and 2.0 wt % crystalline SiO₂. The talcused to prepare Sample 12 of Table 4 includes 74.86 wt % Al₂O₃, 24.7 wt% SiO₂, and a remainder including amounts of TiO₂, Fe₂O₃, CaO, MgO,Na₂O, K₂O, and P₂O₅. The MgTiO₃ used to prepare Sample 12 of Table 4includes 33.2 wt % MgO, 66.2 wt % TiO₂, and the remainder comprisingamounts of Al₂O₃, SiO₂, ZrO₂, BaO, Fe₂O₃, P₂O₅, CaO, Na₂O, and K₂O.

TABLE 4 MgO/ Y₂O₃/ % % Name Al₂O₃ SiO₂ TiO₂ Ta₂O₅ ZrO₂ Other Th. Dporosity Sample 92.33 2.03 0.55/ 0.00/ 3.92 0.09 94 3.10 12 1.00 0.00Sample 91.83 2.00 0.06/ 1.00/ 2.99 0.10 92 3.80 13 0.00 2.00

Table 5 includes samples having TiO₂, Fe₂O₃, or any combination thereof.The starting materials for the samples include an amount of reactiveAl₂O₃, an amount of non-reactive Al₂O₃, or both. For example, Sample 18is prepared with 78.00 wt % reactive Al₂O₃. Additionally, Sample 15 isprepared with 19.98 wt % reactive Al₂O₃ and 59.32 wt % non-reactiveAl₂O₃, Sample 16 is prepared with 23.81 wt % reactive Al₂O₃ Sample 17 isprepared with 19.88 wt % reactive Al₂O₃ and 59.64 wt % non-reactiveAl₂O₃, and Sample 14 is prepared with 19.88 wt % reactive Al₂O₃ and59.64 wt % non-reactive Al₂O₃.

Furthermore, Samples 14, 15, 16, and 17 are prepared with mullite. Inparticular, Sample 14 is prepared with 19.9 wt % mullite. In addition,Sample 15 is prepared with 20.0 wt % mullite, Sample 16 is prepared with4.8 wt % mullite, and Sample 17 is prepared with 19.9 wt % mullite. Themullite used to prepare Sample 14 is CE Minerals/Treibacher WFM Mulliteincluding 76.00 wt % Al₂O₃, 23.50 wt % SiO₂, and a remainder comprisedof Fe₂O₃, CaO, MgO, Na₂O, and K₂O. The mullite used to prepare Samples15 and 16 is Duramul 325/F Mullite including 74.86 wt % Al₂O₃, 24.70 wt% SiO₂, and a remainder comprised of TiO₂, Fe₂O₃, CaO, MgO, Na₂O, K₂O,and P₂O₅. The mullite used to prepare Sample 17 is CE Minerals Mullite70-325 including 67.39 wt % Al₂O₃, 28.38 wt % SiO₂, 2.7 wt % TiO₂, 1.10wt % Fe₂O₃, and a remainder comprised of CaO, MgO, Na₂O, K₂O, and P₂O₅.Additionally, Sample 14 is prepared with 0.6 wt % TiO₂, Sample 47 isprepared with 0.5 wt % TiO₂, and Sample 17 is prepared with 0.6 wt %TiO₂.

TABLE 5 % % Name Al₂O₃ SiO₂ TiO₂ Fe₂O₃ Other Th. D porosity Sample 1494.29 4.68 0.60 0.02 0.28 93 0.34 Sample 15 93.94 4.95 0.51 0.21 0.28 930.30 Sample 16 98.40 1.19 0.00 0.01 0.27 83 12.34 Sample 17 92.58 5.651.14 0.23 0.24 94 0.80 Sample 18 94.31 5.45 0.01 0.02 0.18 91 6.20

TABLE 6 Creep Rate (4 pts Glass Contact Blistering K1C bending)Interface Performance Indentation Name (h⁻¹) (tight/loose) (low/high)(MPa/m^(1/2)) Sample 1 tight low 2.57 Sample 2 2.93 × 10−5 1.89 Sample 55.59 × 10−6 low Sample 6 1.50 × 10−5 tight low 2.27 Sample 7 1.50 × 10−5tight low 2.49 Sample 9 1.20 × 10−6 tight low 2.09 Sample 11 2.40 × 10−6low Sample 15 low Sample 18 3.70 × 10−6 tight high

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed is not necessarily the order inwhich they are performed.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

The specification and illustrations of the embodiments described hereinare intended to provide a general understanding of the structure of thevarious embodiments.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of features is notnecessarily limited only to those features but may include otherfeatures not expressly listed or other features that are inherent tosuch process, method, article, or apparatus. Further, unless expresslystated to the contrary, “or” refers to an inclusive-or and not to anexclusive-or. For example, a condition A or B is satisfied by any one ofthe following: A is true (or present) and B is false (or not present), Ais false (or not present) and B is true (or present), and both A and Bare true (or present).

The use of “a” or “an” is employed to describe elements and componentsdescribed herein. This is done merely for convenience and to give ageneral sense of the scope of the embodiments of the disclosure. Thisdescription should be read to include one or at least one and thesingular also includes the plural, or vice versa, unless it is clearthat it is meant otherwise. The term “averaged,” when referring to avalue, is intended to mean an average, a geometric mean, or a medianvalue. Group numbers corresponding to columns within the Periodic Tableof the elements use the “New Notation” convention as seen in the CRCHandbook of Chemistry and Physics, 81st Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. The materials, methods, andexamples are illustrative only and not intended to be limiting. To theextent not described herein, many details regarding specific materialsand processing acts are conventional and may be found in textbooks andother sources within the refractory objects and glass overflow trougharts.

The specification and illustrations are not intended to serve as anexhaustive and comprehensive description of all of the elements andfeatures of apparatus and systems that use the structures or methodsdescribed herein. Separate embodiments may also be provided incombination in a single embodiment, and conversely, various featuresthat are, for brevity, described in the context of a single embodiment,may also be provided separately or in any subcombination. Further,reference to values stated in ranges includes each and every valuewithin that range. Many other embodiments may be apparent to skilledartisans only after reading this specification. Other embodiments may beused and derived from the disclosure, such that a structuralsubstitution, logical substitution, or another change may be madewithout departing from the scope of the disclosure. Accordingly, thedisclosure is to be regarded as illustrative rather than restrictive.

What is claimed is:
 1. A refractory object comprising: Al₂O₃ at acontent in a range of 90 wt % Al₂O₃ to 94 wt % Al₂O₃; SiO₂ at a contentof at least 2.1 wt % SiO₂; an additive at a content of at least 0.6 wt %additive, wherein the additive includes CaO, MgO, or any combinationthereof, wherein the refractory object comprises no greater than 0.3% wt% ZrO₂.
 2. The refractory object as recited in claim 1, wherein theapparent porosity of the refractory object is no greater than 0.8 vol %.3. The refractory object as recited in claim 1, wherein the refractoryobject includes no greater than 1 wt % of an alkali metal oxide.
 4. Therefractory object as recited in claim 1, wherein the refractory objectincludes at least 0.2 wt % Y₂O₃.
 5. The refractory object as recited inclaim 1, wherein the refractory object includes at least 0.2 wt % TiO₂.6. The refractory object as recited in claim 5, wherein the refractoryobject includes no greater than 4.0 wt % TiO₂.
 7. The refractory objectas recited in claim 1, wherein a fracture toughness of the refractoryobject is at least 2.1 MPa-m^(1/2).
 8. The refractory object as recitedin claim 1, wherein the refractory object further comprises a silicaphase.
 9. The refractory object as recited in claim 1, wherein therefractory object includes a peripheral region disposed between an edgeof the refractory object and a body portion of the refractory object.10. The refractory object as recited in claim 8, wherein a melting pointof the silica phase is at least 1300° C.
 11. The refractory object asrecited in claim 10, wherein the melting point of the silica phase is atleast a sintering temperature used in forming the refractory object. 12.The refractory object as recited in claim 1, wherein the creep rate ofthe refractory object is no greater than 1×10⁻⁴ h⁻¹.